Kinetics of Decomposition of Nitrous Oxide

1978 ◽  
Vol 17 (3) ◽  
pp. 165-169 ◽  
Author(s):  
W. M. Kalback ◽  
C. M. Sliepcevich

The bimolecular reaction 2N 2 O = 2N 2 + 2N 2 was recently shown to belong to the rather rare class of homogeneous reactions. Decomposition of two molecules of nitrous oxide takes place when a collision of a certain critical degree of violence occurs in the gas. At the moment of collision the two molecules must possess a combined energy of at least 58,000 calories (per 2 gram molecules), and it is probable that most of the collision in which this condition is fulfilled are fruitful. A comparison between the kinetics of this homogeneous decomposition and the corresponding reaction proceeding catalytically at the surface of a solid might be expected to throw light on the mechanism of heterogeneous catalysis. Previous efforts ( loc. cit .) to accelerate the reaction catalytically by the introduction of metals into the bulb in which the homogeneous reaction was going on were fruitless, since the reaction, if any, which took place at the surface of the metal was slow in camparison with the gaseous reaction. This difficulty was overcome by using as a catalyst a fine metal wire heated electrically. This could be raised to a sufficiently high temperature to cause the surface reaction to proceed with measurable velocity while the bulk of the gas was kept cold, thus eliminating the homogeneous reaction. Experiments made with platinum wires in this way were successful. The kinetics of the decomposition of nitrous oxide on the surface of platinum are summarized in the equation – d [N 2 O]/ dt = k [N 2 O]/1 + b [O 2 ]. The reaction is unimolecular, but is complicated by the strong retarding action of the oxygen formed.


1964 ◽  
Vol 17 (2) ◽  
pp. 202 ◽  
Author(s):  
TN Bell ◽  
JW Hedger

Ammonia is oxidized by nitrous oxide smoothly and homogeneously at temperatures between 658 and 730� and total pressures up to 250 mm. The products of reaction, nitrogen, water, and hydrazine are accounted for by a free-radical mechanism initiated by oxygen atoms which result from the thermal decomposition of nitrous oxide. Ammonia labelled with the 15N-isotope was used to distinguish between the nitrogen formed from the nitrous oxide and that from the ammonia. The kinetics follow an empirical rate equation, ������������� Rate = k'[N2O]1.56 + k"[N2O]0.61[NH3]. This is of a form which shows the importance of the ammonia molecule participating in the activation of nitrous oxide through bimolecular collision. Assigning a collisional efficiency of unity for like N2O-N2O collisions, the efficiency of ammonia in the process ������������ NH3 + N2O → NH3 + N2O* is determined as 0.85.


1937 ◽  
Vol 15b (6) ◽  
pp. 237-246 ◽  
Author(s):  
E. W. R. Steacie ◽  
H. O. Folkins

The kinetics of the thermal decomposition of nitrous oxide on a silver catalyst has been investigated. The rate of the reaction can be expressed by the equation[Formula: see text]It may therefore be concluded that the nitrous oxide is slightly adsorbed by the catalyst, while oxygen is fairly strongly adsorbed and retards the reaction. Added oxygen affects the reaction in the manner predicted by the rate equation, in contrast to its behavior on a platinum catalyst as previously found by Steacie and McCubbin.


1936 ◽  
Vol 14b (3) ◽  
pp. 84-89 ◽  
Author(s):  
E. W. R. Steacie ◽  
J. W. McCubbin

Further experiments have been made on the kinetics of the decomposition of nitrous oxide on the surface of platinum. Observations on the effect of foreign gases confirm the previous conclusion that inert gases may exert a surprisingly large retarding effect by hindering the diffusion of the reactant to the more remote parts of a porous catalyst.Adsorption measurements have also been made, and their bearing on the mechanism of the reaction is discussed.


1994 ◽  
Vol 59 (9) ◽  
pp. 2029-2041
Author(s):  
Oldřich Pytela ◽  
Taťjana Nevěčná

The kinetics of decomposition of 1,3-bis(4-methylphenyl)triazene catalyzed with 13 substituted benzoic acids of various concentrations have been measured in 25 vol.% aqueous methanol at 25.0 °C. The rate constants observed (297 data) have be used as values of independent variable in a series of models of the catalyzed decomposition. For the catalytic particles were considered the undissociated acid, its conjugated base, and the proton in both the specific and general catalyses. Some models presumed formation of reactive or nonreactive complexes of the individual reactants. The substituent effect is described by the Hammett equation. The statistically best model in which the observed rate constant is a superposition of a term describing the dependence on proton concentration and a term describing the dependence on the product of concentrations of proton and conjugated base is valid with the presumption of complete proton transfer from the catalyst acid to substrate, which has been proved. The behaviour of 4-dimethylamino, 4-amino, and 3-amino derivatives is anomalous (lower catalytic activity as compared with benzoic acid). This supports the presumed participation of conjugated base in the title process.


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